The present invention relates to synthetic based lubricants which are particularly useful for lubricating heavy duty diesel engines.
Specifications for modern engine lubricants, such as those for heavy duty diesel engines, especially in Europe, indicate a longer interval between oil changes than has been customary in the past. In order to formulate engine oils with longer drain intervals, higher levels of certain additives have been incorporated, typically greater than 1.7% by weight detergent substrate and greater than 10 TBN (Total Base Number, ASTM D2896) in the finished lubricant. Additionally, synthetic base stocks have been used to improve the thermo-oxidative stability of the base oils. These high levels of detergent soap substrate and TBN provide improved piston cleanliness and reduced engine wear over drain intervals which may be in excess of 100,000 km. However, the high level of detergent can cause higher levels of valve train wear, as measured in the Cummins M11 valve train wear test.
To address the problem of increased valve train wear, a heavy duty diesel lubricant has now been formulated using a selection of synthetic base oils, a dispersant-viscosity modifier, and a sulfur-free functionalized alkyl phenol detergent. The preferred lubricant also exhibits good emissions performance.
U.S. Pat. No. 5,719,107, Outten et al., Feb. 17, 1998, discloses a crankcase lubricant for diesel engines, comprising an admixture of a major amount of an oil of lubricating viscosity, at least 4 mass % dispersant, at least 0.3 mass % of a metal phenate, which may be neutral or overbased, and various other components. The oil can be any of the synthetic or natural oils, or mixtures. The oil has a viscosity of about 2.5 to about 12 mm2/sec. Multifunctional viscosity modifiers that also function as dispersants are also disclosed. Suitable metal phenates include calcium, magnesium, and mixtures of the two.
U.S. Pat. No. 2,647,873, Matthews et al., Aug. 4, 1953, discloses compounds which are suitable as additional agents to lubricating oils and greases. Metal salts and condensates are prepared from the following ingredients: an aromatic compound containing a polar radical or radicals (e.g., phenols), and aldehydes such as formaldehyde. The Ca, Mg, Sr, Cu, Zn, Al, and Sn salts of certain of these condensation products are disclosed.
The present invention provides a lubricant suitable for use in a diesel engine, comprising:
(a) a synthetic base oil composition, said base oil overall having a kinematic viscosity of at least 4.8xc3x9710xe2x88x926m2/s (4.8 cSt) at 100xc2x0 C. and a viscosity index of at least 110;
(b) a dispersant-viscosity modifier; and
(c) a sulfur-free functionalized hydrocarbyl (or alternatively, alkyl) phenol detergent.
The invention also provides a method for lubricating a crankcase-lubricated diesel engine comprising supplying such a lubricant to the crankcase thereof.
Various preferred features and embodiments will be described below by way of non-limiting illustration.
The first component of the present lubricants is a selected synthetic base oil or mixture of base oils. Synthetic oils in general include hydrocarbon oils such as polymerized and interpolymerized olefins, e.g., polyalphaolefins (PAOs). Typically, polyalphaolefins are derived from monomers having from about 4 to about 30, or from about 4 to about 20, or from about 6 to about 16 carbon atoms. Typically, PAOs are hydrogenated. Examples of useful PAOs polybutylenes, polypropylenes, propylene-isobutylene copolymers, poly(1-hexenes, poly(1-octenes), poly(1-decenes),and mixtures thereof).
Alkylbenzenes are another species of synthetic hydrocarbon oil. Alkylbenzenes include generally C10-13 alkyl-substituted benzenes, including dodecylbenzenes and bisdodecylbenzenes such as m-bisdodecylbenzene; tetradecylbenzenes; dinonylbenzenes; and di(2-ethylhexyl)-benzenes;
Other species of synthetic hydrocarbon oils include polyphenyls (e.g., biphenyls, terphenyls, and alkylated polyphenyls), alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs, and homologues thereof.
Group III base oils are also sometimes considered to be synthetic base oils, and for the purposes of this invention they can be considered to be included within the definition of xe2x80x9csynthetic base oils.xe2x80x9d Group III base oils are defined by the API Base Oil Interchange Guidelines as having the following minimum characteristics: xe2x89xa60.03% sulfur, xe2x89xa790% saturates, and xe2x89xa7120 viscosity index. These are generally oils which are derived from natural stocks (as opposed to being derived from synthetic sources), but are so highly refined that they can exhibit the performance and viscosity parameters of other synthetic base oils.
Another class of synthetic base oils includes alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, or similar reaction constitute. These are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methylpolyisopropylene glycol ether having an average molecular weight of 1,000 diphenyl ether of polyethylene glycol having a molecular weight of 500-1,000, diethyl ether of polypropylene glycol having a molecular weight of 1,000-1,500) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid esters, or the C13 Oxo acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating oils comprises synthetic esters, including the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, dodecanedioic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, and alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, and propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Examples of synthetic monoester oils which are commercially available include Emery(trademark) 2935, Emery(trademark) 2971, Priolube(trademark) 1976, Priolube(trademark) 3999, Nycobase(trademark) 8311, Nycobase(trademark) 8885, and Nycobase(trademark) 8886.
A useful synthetic base oil composition is selected from one or more polyalphaolefin oils, one or more synthetic esters, and one or more alkylbenzenes, or mixtures thereof. In one embodiment the base oil is a mixture of a polyalphaolefin oil having a viscosity of 4 to 8xc3x9710xe2x88x926m2/s (4-8 cSt) at 100xc2x0 C., alternatively in an amount of 60 to 95% by weight, a C10-13 alkyl-substituted benzene, or in an amount of 5 to 20 percent by weight, and optionally a synthetic monoester, for instance, in an amount of 0 to 20 percent by weight.
The synthetic base oil composition used in the present lubricant should exhibit a kinematic viscosity (ASTM 445) of at least 4.8xc3x9710xe2x88x926 m2/s (4.8 cSt) at 100xc2x0 C. and alternatively at least 5.0, 5.1 or 5.3, and optionally up to 7.0xc3x9710xe2x88x926m2/s at 100xc2x0 C. The base oil composition overall should also exhibit a viscosity index (ASTM 2270) of at least 110, such as at least 120, or in the range of 120 to 160. Viscosity Index or xe2x80x9cV.I.xe2x80x9d is an arbitrary number which indicates the resistance of a lubricant to viscosity change with temperature. The Dean and Davis viscosity index calculated from the observed viscosities of a lubricant at 40xc2x0 C. and 100xc2x0 C. gives V.I. values ranging from 0 or negative values to values of 200 or more. The higher its V.I. value, the greater the resistance of a lubricant to thicken at low temperatures and thin out at high temperatures. These parameters are intended to apply the base oil composition as such, without the benefit of any viscosity index modifiers (which may, however, also be present).
Moreover, in one embodiment, most or all of the individual components of the synthetic base oil exhibit these same viscosity and viscosity index properties. Thus, any components of the oil which individually have a viscosity index of less than 120 can optionally comprise in total no more than 20 percent, and in one embodiment no more than 10 percent by weight of the base oil composition. Moreover, in one embodiment, at most a small portion of the overall base oil composition will comprise a natural (i.e., non-synthetic) oil. This option may be desired because natural oils generally do not exhibit the desirable viscosity or viscosity index properties. Therefore, the base oil composition can contain 1 to 25 percent by weight of natural base oil components, or less than 20 percent, or less than 10 percent, and in one embodiment can contain substantially no natural base oil components (e.g., less than 5% or less than 1%). For purposes of determining the amount of natural base oil, the amount of natural base oils present as diluent oils normally present in the various additives is to be taken into account. These materials can typically contribute 5 to 10 percent or more of oil to the overall composition.
A second component of the lubricant of the present invention is a dispersant viscosity index modifier. Multifunctional additives that provide both viscosity improving properties and dispersant properties are known in the art and are commercially available. Such products are described in numerous publications including Dieter Klamann, xe2x80x9cLubricants and Related Productsxe2x80x9d, Verlag Chemie Gmbh (1984), pp 185-193; C. V. Smalheer and R. K. Smith xe2x80x9cLubricant Additivesxe2x80x9d, Lezius-Hiles Co. (1967); M. W. Ranney, xe2x80x9cLubricant Additivesxe2x80x9d, Noyes Data Corp. (1973), pp 92-145, M. W. Ranney, xe2x80x9cLubricant Additives, Recent Developmentsxe2x80x9d, Noyes Data Corp (1978), pp 139-164; M. W. Ranney, xe2x80x9cSynthetic Oils and Additives for Lubricantsxe2x80x9d, Noyes Data Corp. (1980), pp 96-166; and the above-identified U.S. Pat. No. 5,719,107.
Dispersant viscosity index modifiers are generally one or a mixture of polymers which perform several functions. They serve first as a viscosity index (xe2x80x9cVIxe2x80x9d) modifier, sometimes referred to as a viscosity index improver. This is the well-known function of controlling the rate or amount of viscosity change of a lubricant as a function of temperature. These are materials which have comparatively little thickening effect at low temperatures but significant thickening at high temperatures. This behavior extends the temperature range over which a lubricant can be used.
The VI modifiers for which the present invention is particularly useful further contain functional groups which provide dispersant functionality (and sometimes other functionality, such as antioxidation properties) to the lubricant composition. Dispersant functionality serves to prevent particulate contamination in an oil or other lubricant from agglomerating into larger particles which can settle out as sludge or varnish. Although separate dispersant additives can also be used in the present invention, the presence of one or more comonomers on the VI modifier entity which serve this function is desirable.
The dispersant viscosity index modifiers can be functionalized versions of polymers which are generally used as viscosity index modifiers. Among the common classes of such polymers are olefin copolymers and acrylate or methacrylate copolymers.
Functionalized olefin copolymers can be, for instance, interpolymers of ethylene and propylene which are grafted with an active monomer such as maleic anhydride and then derivatized with an alcohol or an amine, as described in U.S. Pat. No. 4,089,794. Other such copolymers are copolymers of ethylene and propylene which are reacted or grafted with nitrogen compounds, as described in U.S. Pat. No. 4,068,056. Vinyl pyridine, N-vinyl pyrrolidone and N,Nxe2x80x2-dimethylaminoethyl methacrylate are examples of typical nitrogen-containing monomers.
Derivatives of polyacrylate esters are well-known as dispersant viscosity index modifier additives. Dispersant acrylate or polymethacrylate viscosity modifiers such as Acryloid(trademark) 985, Viscoplex(trademark) 6-054, or Viscoplex(trademark) 2-500, from RohMax, or LZ(copyright) 7720C, from The Lubrizol Corporation, are particularly useful.
The amount of the dispersant viscosity modifier should be an amount suitable to provide a desirable overall viscosity index as well as to impart dispersancy to the formulation. The desired degree of dispersancy (which can also be provided in part by conventional dispersants) is that which will permit the oil formulation to meet the requirements of soot handling, such as that measured in the Mack T8-E test for Mack EOxe2x88x92M+ specification, while maintaining good piston cleanliness and seal compatibility, in accordance with the Mercedes Benz 228.5 specifications. The amount of the dispersant viscosity modifier is typically 0.5 to 3 weight percent of the lubricant, such as 1 to 2 percent by weight, or 0.3 to 1.6 percent by weight.
The final required component of the present invention is a sulfur-free functionalized alkyl phenol detergent. Detergents in general are extremely well known additives for engine oil lubricants. They are generally salts of organic acids, which are often overbased. Metal overbased salts of organic acids are widely known to those of skill in the art and generally include metal salts wherein the amount of metal present exceeds the stoichiometric amount. Such salts are said to have conversion levels in excess of 100% (i.e., they comprise more than 100% of the theoretical amount of metal needed to convert the acid to its xe2x80x9cnormalxe2x80x9d or xe2x80x9cneutralxe2x80x9d salt). They are commonly referred to as overbased, hyperbased or superbased salts and are usually salts of organic sulfur acids, organic phosphorus acids, carboxylic acids, phenols or mixtures of these.
The terminology xe2x80x9cmetal ratioxe2x80x9d is used to designate the ratio of the total chemical equivalents of the metal in the overbased salt to the chemical equivalents of the metal in the salt which would be expected to result in the reaction between the organic acid to be overbased and the basic reacting metal compound according to the known chemical reactivity and stoichiometry of the two reactants. Thus, in a normal or neutral salt the metal ratio is one and, in an overbased salt, the metal ratio is greater than one. The overbased salts usually have metal ratios of at least 1.1:1. Typically they have ratios of 2:1 or 3:1 to 40:1. Salts having ratios of 12:1 to 20:1 are often used.
The basically reacting metal compounds used to make the overbased salts are usually an alkali or alkaline earth metal compound (i.e., the Group IA, IIA, and IIB metals, but normally excluding francium and radium and typically also excluding rubidium, cesium and beryllium), although other basically reacting metal compounds can be used. Compounds of Ca, Ba, Mg, Na and Li, such as their hydroxides and alkoxides of lower alkanols are usually used as basic metal compounds in preparing these overbased salts but others can be used as shown by the prior art referred to herein. Overbased salts containing a mixture of ions of two or more of these metals can be used in the present invention.
Overbased materials are generally prepared by reacting an acidic material (typically an inorganic acid or lower carboxylic acid, such as carbon dioxide) with a mixture comprising an acidic organic compound, a reaction medium comprising at least one inert, organic solvent (mineral oil, naphtha, toluene, xylene, etc.) for said acidic organic material, a stoichiometric excess of a metal base, and a promoter. The acidic organic compound will, in the present instance, be the functionalize alkyl phenol.
The acidic material used in preparing the overbased material can be a liquid such as formic acid, acetic acid, nitric acid, or sulfuric acid. Acetic acid is particularly useful. Inorganic acidic materials can also be used, such as HCl, SO2, SO3, CO2, or H2S, and in one embodiment, CO2 or mixtures thereof, e.g., mixtures of CO2 and acetic acid.
A promoter is a chemical employed to facilitate the incorporation of metal into the basic metal compositions. The promoters are diverse and are well known in the art and includes lower alcohols. A discussion of suitable promoters is found in U.S. Pat. Nos. 2,777,874, 2,695,910, and 2,616,904. Patents specifically describing techniques for making basic salts of acidic organic compounds generally include U.S. Pat. Nos. 2,501,731; 2,616,905; 2,616,911; 2,616,925; 2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,318,809; 3,488,284; and 3,629,109.
The detergents useful in the present invention are sulfur-free functionalized alkyl phenol detergents (phenates). The use of the terms xe2x80x9cphenolxe2x80x9d and xe2x80x9cphenatexe2x80x9d is not intended to imply that the aromatic moiety is limited to alkyl phenol per se, that is, a single benzene ring substituted with an OH group and an alkyl group, although, in fact, this is a particularly useful species upon which the substituted phenol is constructed. Other aromatic species which are encompassed within the scope of the present invention include those containing more than one OH group, such as catechols; phenolic species containing multiple alkyl or hydrocarbyl substituents; multiple ring structures including fused ring structures, comprising both unsaturated fused rings (e.g., naphthalene-based) and saturated rings (e.g., tetrahydronaphthalene); and non-condensed multiple ring structures including phenyl substitution and phenylalkyl substitution.
The functionalization of the alkyl phenol can comprise the addition of any functional group to the phenolic compound, other than an additional hydroxy group or an additional hydrocarbyl group, at least one such alkyl or hydrocarbyl group already being present in sufficient amount to provide oil solubility to the detergent. Typical functional groups include t-butyl groups, methylene coupling groups, ester-substituted alkyl groups, and aldehyde groups. In one embodiment the functionalization is by addition of carboxy functionality, in which case the detergent can be an alkyl salicylate or a derivative thereof. Salicylate detergents are well known; see, for instance, U.S. Pat. Nos. 5,688,751 or 4,627,928. In another embodiment, the substituent can be based on a glyoxylic acid condensation. Glyoxylic acid itself is HC(xe2x95x90O)xe2x80x94CO2H; related ketones of the structure R1C(xe2x95x90O)xe2x80x94CO2H are also contemplated; thus R1 can be hydrogen or a hydrocarbyl group of, for instance, 1 to 20 carbon atoms. A typical glyoxylate condensation product is 
shown here as an anionic species, which will typically be neutralized with a metal salt. In this structure, the R groups are alkyl groups. The material shown would be the condensation of 2 moles of alkyl phenol with 1 mole of glyoxylic acid or derivative thereof. Other molar ratios are also possible; when a 1:1 ratio is approached, the condensation product becomes oligomeric or polymeric. These materials and methods for their preparation are disclosed in greater detail in U.S. Pat. No. 5,356,546.
In other embodiments the functionalized alkyl phenol can be a condensation product of the alkyl phenol with formaldehyde or other lower aldehydes. The acidic substituent, in this case, would be considered to be the one or more additional phenolic groups. The simplest such condensation product would be 
shown here as the 2:1 molar condensate of phenol:formaldehyde. Also, depending on the conditions of reaction, the formaldehyde unit may appear in other oxidation states. As in the case of glyoxylates, oligomeric structures can be formed when the molar ratio of formaldehyde:phenol increases. Examples of such type of oligomeric species are the calixarates, which are cyclic materials containing 4 to 8 phenol-formaldehye repeat units. Calixarates and methods of their preparation are disclosed in greater detail in U.S. Pat. No. 5,114,601. As will be apparent, mixtures of formaldehyde, other aldehydes, and glyoxylic acid can also be employed in such condensation reactions.
One category of functionalized derivatives of alkyl phenols, however, are certain saligenen derivatives. Saligenin itself, also known as salicyl alcohol and o-hydroxybenzyl alcohol, is represented by the structure 
Useful saligenin derivatives include certain metal saligenin derivative which function as detergents.
A general example of such a saligenin derivative can be represented by the formula 
wherein X comprises xe2x80x94CHO or xe2x80x94CH2OH, Y comprises xe2x80x94CH2xe2x80x94 or xe2x80x94CH2OCH2xe2x80x94, and wherein such xe2x80x94CHO groups comprise at least about 10 mole percent of the X and Y groups; M is hydrogen, ammonium, or a valence of a metal ion, R1 is a hydrocarbyl group containing 1 to about 60 carbon atoms, m is 0 to about 10, and each p is independently 0, 1, 2, or 3, provided that at least one aromatic ring contains an R1 substituent and that the total number of carbon atoms in all R1 groups is at least 7. When m is 1 or greater, one of the X groups can be hydrogen.
As used herein, the expression xe2x80x9crepresented by the formulaxe2x80x9d indicates that the formula presented is generally representative of the structure of the chemical in question. However, it is well known that minor variations can occur, including in particular positional isomerization, that is, location of the X, Y, and R groups at different position on the aromatic ring from those shown in the structure. The expression xe2x80x9crepresented by the formulaxe2x80x9d is expressly intended to encompass such variations.
When the metal is magnesium, these compounds can be represented by the formula 
This represents generally a metal salt, such as a magnesium salt, of a compound containing one aromatic ring or a multiplicity of aromatic rings linked by xe2x80x9cYxe2x80x9d groups, and also containing xe2x80x9cXxe2x80x9d groups. (Mg) represents a valence of a magnesium ion, and n, in each instance, is 0 or 1. (When n is zero the Mg is typically replaced by H to form an xe2x80x94OH group.) The value for xe2x80x9cmxe2x80x9d is typically 0 to 10, so number of such rings will be 1 to 11, although it is to be understood that the upper limit of xe2x80x9cmxe2x80x9d is not a critical variable. In one embodiment m is 2 to 9, such as 3 to 8 or 4 to 6. Other metals include alkali metals such as lithium, sodium, or potassium; alkaline earth metals such as calcium or barium; and other metals such as copper, zinc, and tin.
Most of the rings contain at least one R1 substituent, which is the afore-mentioned hydrocarbyl group, such as alkyl group. R1 can contain 1 to 60 carbon atoms, such as 7 to 28 carbon atoms or 9 to 18 carbon atoms. Of course it is understood that R1 will normally comprise a mixture of various chain lengths, so that the foregoing numbers will normally represent an average number of carbon atoms in the R1 groups (number average). Each ring in the structure will be substituted with 0, 1, 2, or 3 such R1 groups (that is, p is 0, 1, 2, or 3), most typically 1, and of course different rings in a given molecule may contain different numbers of such substituents. At least one aromatic ring in the molecule must contain at least one R1 group, and the total number of carbon atoms in all the R1 groups in the molecule should be at least 7, such as at least 12.
In the above structure the X and Y groups may be seen as groups derived from formaldehyde or a formaldehyde source, by condensative reaction with the aromatic molecule. The relative amounts of the various X and Y groups depends to a certain extent on the conditions of synthesis of the molecules. While various species of X and Y may be present in the molecules in question, the commonest species comprising X are xe2x80x94CHO (aldehyde functionality) and xe2x80x94CH2OH (hydroxymethyl functionality); similarly the commonest species comprising Y are xe2x80x94CH2xe2x80x94 (methylene bridge) and xe2x80x94CH2OCH2xe2x80x94 (ether bridge). The relative molar amounts of these species in a sample of the above material can be determined by 1H/13 C NMR as each carbon and hydrogen nucleus has a distinctive environment and produces a distinctive signal. (The signal for the ether linkage, xe2x80x94CH2OCH2xe2x80x94 must be corrected for the presence of two carbon atoms, in order to arrive at a correct calculation of the molar amount of this material. Such a correction is well within the abilities of the person skilled in the art.)
In one embodiment, X is at least in part xe2x80x94CHO and such xe2x80x94CHO groups comprise at least 10, 12, or 15 mole percent of the X and Y groups. In another embodiment the xe2x80x94CHO groups comprise 20 to 60 mole percent of the X and Y groups, such as 25 to 40 mole percent of the X and Y groups.
In another embodiment, X is at least in part xe2x80x94CH2OH and such xe2x80x94CH2OH groups comprise 10 to 50 mole percent of the X and Y groups, such as 15 to 30 mole percent of the X and Y groups.
In an embodiment in which m is non-zero, Y is at least in part xe2x80x94CH2xe2x80x94 and such xe2x80x94CH2xe2x80x94 groups comprise 10 to 55 mole percent of the X and Y groups, such as 25 to 45 or 32 to 45 mole percent of the X and Y groups.
In another embodiment Y is at least in part xe2x80x94CH2OCH2xe2x80x94 and such xe2x80x94CH2OCH2xe2x80x94 groups comprise 5 to 20 mole percent of the X and Y groups, such as 10 to 16 mole percent of the X and Y groups.
The above-described compound is, as mentioned, typically a magnesium salt and, indeed, the presence of magnesium during the preparation of the condensed product is believed to be useful in achieving the desired ratios of X and Y components described above. The number of Mg ions in the compound is characterized by an average value of xe2x80x9cnxe2x80x9d of 0.1 to 1 throughout the composition, such as 0.2 or 0.3 to 0.4 or 0.5, or 0.35 to 0.45. Since Mg is normally a divalent ion, when all of the phenolic structures shown are entirely neutralized by Mg+2 ions, the average value of n in the composition will be 0.5, that is, each Mg ion neutralizes 2 phenolic hydroxy groups. Those two hydroxy groups may be on the same or on different molecules. If the value of n is less than 0.5, this indicates that the hydroxy groups are less than completely neutralized by Mg ions. If the value of n is greater than 0.5, this indicates that a portion of the valence of the Mg ions is satisfied by an anion other than the phenolic structure shown. For example each Mg ion could be associated with one phenolic anion and one hydroxy (OHxe2x88x92) ion, to provide an n value of 1.0. The specification that n is 0.1 to 1.0 is not directly applicable to overbased versions of this material (described below and also a part of the present invention) in which an excess of Mg or another metal can be present.
It is understood that in a sample of a large number of molecules, some individual molecules may exist which deviate from these parameters, for instance, there may be some molecules containing no R1 groups whatsoever. These molecules could be considered as impurities, and their presence will not negate the present invention so long as the majority (and generally the substantial majority) of the molecules of the composition are as described.
The above-described component can be prepared by combining a phenol substituted by the above-described R1 group with formaldehyde or a source of formaldehyde and magnesium oxide or magnesium hydroxide under reactive conditions, in the presence of a catalytic amount of a strong base. Common reactive equivalents of formaldehyde includes paraformaldehyde, trixoane, formalin and methal. For convenience, paraformaldehyde is can be used.
The relative molar amounts of the substituted phenol and the formaldehyde can be important in providing products with the desired structure and properties. In a typical embodiment, the substituted phenol and formaldehyde are reacted in equivalent ratios of 1:1 to 1:3 or 1.4, such as 1:1.1 to 1:2.9 or 1:1.4 to 1:2.6, or 1:1.7 to 1:2.3. Thus in one embodiment there will be about a 2:1 equivalent excess of formaldehyde. (One equivalent of formaldehyde is considered to correspond to one H2CO unit; one equivalent of phenol is considered to be one mole of phenol.)
The strong base is can be sodium hydroxide or potassium hydroxide, and can be supplied in an aqueous solution.
The process can be conducted by combining the above components with an appropriate amount of magnesium oxide or magnesium hydroxide with heating and stirring. A diluent such as mineral oil or other diluent oil can be included to provide for suitable mobility of the components. An additional solvent such as an alcohol can be included if desired, although it is believed that the reaction may proceed more efficiently in the absence of additional solvent. The reaction can be conducted at room temperature or at a slightly elevated temperature such as 35-120xc2x0 C., 70-110xc2x0 C., or 90-100xc2x0 C., and of course the temperature can be increased in stages. When water is present in the reaction mixture it is convenient to maintain the mixture at or below the normal boiling point of water. After reaction for a suitable time (e.g., 30 minutes to 5 hours or 1 to 3 hours) the mixture can be heated to a higher temperature, typically under reduced pressure, to strip off volatile materials. Favorable results are obtained when the final temperature of this stripping step is 100 to about 150xc2x0 C., such as 120 to about 145xc2x0 C.
Reaction under the conditions described above typically leads to a product which has a relatively high content of xe2x80x94CHO substituent groups, that is, 10%, 12%, and even 15% and greater. Such materials, when used as detergents in lubricating compositions, exhibit good upper piston cleanliness performance, low Cu/Pb corrosion, and good compatibility with seals. Use of metals other than magnesium in the synthesis typically leads to a reduction in the content of xe2x80x94CHO substituent groups.